KR102402926B1 - Composition for rheology control - Google Patents

Abstract

The present invention relates to i) 15 to 95% by weight of the amide compound (A), ii) 5 to 75% by weight of the urea compound (B), iii) 0 to 50% by weight of the ionogen compound (C), and iv) 0 to It relates to a rheology modifier containing 35% by weight of an organic solvent (D).

Description

Composition for rheology control {COMPOSITION FOR RHEOLOGY CONTROL}

The present invention relates to compositions and uses thereof, and to formulations containing said compositions.

To control the rheology of liquid systems, in particular liquid coating systems, organically modified bentonites, silicas, hydrogenated castor oil and polyamide waxes are used in principle.

One drawback to the use of such flow aids is that they are usually available in the form of anhydrous solids. Consequently, as a result, the flow aid must be broken down prior to use with the aid of solvents and shear forces to form a semifinished product. Alternatively, flow aids may also be used, without degradation, by introducing them into the liquid coating system by targeted temperature control. If this temperature control does not occur according to the target setting, microcrystals typically result in the finished coating system, which can cause coating defects.

One general disadvantage of the use of such flow aids is that they cause haze and haze in clear, transparent coatings. Also, handling dry powder products is undesirable as they can generate dust during processing.

An alternative liquid application to these rheology modifiers is provided by solutions of certain urea compounds. Such solutions are often used in practice and are described, for example, in EP 1 188 779. Typical solvents or carrier media are in fact polar/aprotic and/or so-called ionic liquids which represent typical molten salts, which are liquids under moderate temperature conditions (generally below 80° C., ideally at room temperature). Admittedly, the rheology control properties of dissolved urea compounds are usually very good, but in many cases there is a need for more optimized rheology control behavior. Optimal behavior is often seen in improved flow efficacy, as well as improved compatibility in formulations that in some cases relate to applications (eg, binders).

WO2011/091812 relates to the use of urea compounds and amide compounds in fire resistant coatings. The disadvantage is that the urea compound and the amide compound must be separated from each other and put into the fire resistant coating due to their mutual incompatibility, so coating manufacturers cannot use them as additive mixtures.

Accordingly, it is an object of the present invention to provide a rheology modifier that can be used universally and practically and is of excellent quality.

The solution to this problem is

i) from 15 to 95% by weight of the amide compound (A),

ii) from 5 to 75% by weight of the urea compound (B),

iii) 0 to 50% by weight of the ionogen compound (C) and

iv) 0 to 35% by weight of organic solvent (D)

A composition containing

The amide compound (A) has a molar mass of 70 to 600 g/mol, the amide compound (A) includes at most one amide group in which hydrogen is bonded to a nitrogen atom, and the amide compound (A) is urethane Free from baby, phosphorus, silicon and halogen, the amide compound (A) is represented by the following formula (I):

[During the ceremony,

Xx is the same or different and is according to one of the formulas RzC(=O)-NRaRb (Xx1), RaC(=O)-NRzRb (Xx2) and RbC(=O)-NRzRa (Xx3) and is Rz, Ra and Rb and an amide group C (= O) -N combined with

Xy is the same or different and is according to one of the general formulas RzC(=O)-NRcRd(Xy1), RcC(=O)-NRzRd(Xy2) and RdC(=O)-NRzRc(Xy3) and Rz, Rc and Rd is an amide group C (= O) -N combined with

each Rz is the same or different and is a branched or unbranched hydrocarbon radical having from 1 to 32 carbon atoms, saturated or unsaturated, which may contain amino groups and/or amide groups as groups containing heteroatoms,

Ra, Rb, Rc, and Rd are each the same or different and each independently of the other is hydrogen and/or an organic radical containing 1 to 16 carbon atoms, branched or unbranched, saturated or unsaturated, provided that

Ra, Rb, Rc and Rd have a total of 4 or more carbon atoms,

at most one of the residues selected from the groups Ra, Rb, Rc and Rd is in the form of hydrogen,

Ra and Rb and/or Rc and Rd, together with the CO-N group bonding to Ra and Rb and/or Rc and Rd, form a ring according to formula (α-1) and having 4 to 10 ring atoms can and/or:

,

,

Ra and Rb and/or Rc and Rd, together with the N-atoms bonded to Ra and Rb and/or Rc and Rd, form a ring according to formula (ß-1) and having 4 to 7 ring atoms can be:

, 또는

, or

Rb and Rc, respectively, taken together with the N-atom and the Rz moiety bonded to Rb and Rc, may form a ring having 5 to 7 ring atoms according to formula (γ-1):

,

,

Ra, Rb, Rc, Rd and Rz have a total of up to 36 carbon atoms and up to 8 heteroatoms selected from the groups N and O];

The urea compound (B) has a molecular weight of at least 350 g/mol and has at least one urea group,

The ionogen compound (C) contains cationic and anionic components, and is different from the amide compound (A) and the urea compound (B);

The organic solvent (D) does not contain a urea group or an ionic group, and has at most two heteroatoms selected from the group consisting of nitrogen and oxygen.

Components (A), (B), (C) and/or (D) may each exist in the form of different species, ie as mixtures. The composition according to the present invention may optionally contain other components in addition to components (A), (B), (C) and (D).

The molecular weight of the relevant urea compounds (B) according to the invention is limited in the low molecular weight range, since urea compounds (B) with a molar mass of less than 350 g/mol generally have little or no rheological effect. . These low-effect or ineffective substances having a molecular weight of less than 350 g/mol are usually specific monomeric or low-molecular-weight oligomeric compounds having a given molecular weight, so that these compounds generally do not have molecular heterogeneity, and therefore a weight average molecular weight or number average It is not necessary to state the molecular weight. Accordingly, the lower limit of 350 g/mol, chosen as required, is the actual molecular weight of the species and can be determined, for example, by NMR.

The upper limit of the molecular weight of the urea compound (B) is not critical as long as there is compatibility between the urea compound (B) and other components of the rheology modifier and the subsequent formulation in which the urea compound (B) is used. General compatibility limits are usually reached with the polymeric urea compound (B), for which reason only average molecular weights can be described. Usually, as the urea compound (B), it is suitable to have a weight average molecular weight of less than 60000 g/mol, but in each case urea having a high molecular weight, for example 80000 or 100000 g/mol, as long as compatibility is ensured in the system concerned. Compounds may also be used. When compatibility is insufficient, a person skilled in the art uses the urea compound (B) having a low weight average molecular weight without delay. However, the synthesis of the urea compound (B) having a weight average molecular weight well above 100000 g/mol is not a general problem for the person skilled in the art.

It is known to the person skilled in the art that for the high molecular weight range other methods are preferred instead of NMR-spectroscopy for molecular weight determination. The measurement of the weight average molecular weight of the urea compound (B) having a molar mass of more than 1000 g/mol is made as a weight average of the molar mass distribution measured by gel permeation chromatography (GPC) according to the following disclosure. The GPC-molar mass distribution is determined according to DIN 55672 part 2 of January 2008. A solution of lithium bromide (content 5 g/l) in dimethylacetamide is used as eluent. For calibration, a polymethylmethacrylate-standard of narrowly dispersed linear structure with a molecular weight of 1000000 to 102 g/mol is used. The temperature of the entire GPC-system (injector, sample distributor, detector and column) is 80°C. The weight average molar mass of the urea compound (B) of 350 g/mol to about 1000 g/mol is determined, for example, by NMR taking the integration of the corresponding NMR-resonance signal into account. However, according to the present invention, it is only necessary to ensure that the urea compound (B) has a molecular weight of at least 350 g/mol as described above, so the selection of the measuring method is not important in this range.

Accordingly, in a particularly preferred embodiment of the present invention 70 to 100% by weight of the urea compound (B) has a molecular weight of at least 350 g/mol to a maximum of 60000 g/mol.

The composition according to the present invention is an easy-to-apply formulation, which can be prepared in liquid form. End users (eg users or manufacturers of coats, plastics or adhesives) can simply use the additive with less risk of misuse. Because the rheological effect additive components (A) and (B) are present as a mixture, storage costs for the custodian are reduced (only one storage location for (A) and (B)), requiring fewer components to be administered Therefore, it is possible to accelerate the coating production. The composition according to the invention stands out for its good storage stability and universal applicability in different systems (eg in different types of binders).

The composition according to the invention shows a particularly good rheological effect. For example, the rheological effect of a composition can be measured based on the gel strength or sag resistance (sag limit) of the corresponding coating formulation. In addition, the compositions according to the invention exhibit broad compatibility (criteria: eg the formation of droplets, hazing and/or turbidity in the formulations) in which they are applied (eg binders).

The cooperation of the two active ingredients, which are rheologically active, namely the amide compound (A) and the urea compound (B), is decisive for the theoretical dose and suitability as a rheology modifier.

In addition to the components (A), (B), (C) and (D) described above, the composition according to the present invention may contain components different from each of these components. Substantially, these components (each of A, B, C and D) and said different components do not degrade the quality of the composition according to the invention. The aforementioned degradation relates to suitability as a (rheological) additive. If the composition according to the present invention has an excessively large proportion of less inactive components (eg functional groups capable of causing cross-linking reactions), the quality may deteriorate (eg, due to poor storage stability). In addition, the composition according to the invention should be able to handle easily with respect to the application and should contain as little as possible components which are not useful for use as additives. Based on the above, first, the components different from each of A, B, C and D are described as follows:

- each of A, B, C and D and said different components in the composition according to the invention preferably total up to 50% by weight, particularly preferably up to 30% by weight, very particularly preferably up to 20% by weight , particularly preferably up to 10% by weight. In other specific embodiments it contains up to 5% by weight and up to 3% by weight. In another particularly preferred embodiment the composition is substantially free of components different from each of A, B, C and D.

- each of A, B, C and D and said different components in total preferably have a hydroxyl number of less than 15 mg KOH/g (if a corresponding hydroxyl-containing species is present).

- each of A, B, C and D and said different components are preferably not present as so-called crosslinking agents. The crosslinking agents here are, for example, polyisocyanates, amino resins such as melamine resins, urea-formaldehyde resins and benzoguanamine resins, polyamides and polyepoxides.

- The composition according to the invention preferably does not contain pigments and solid fillers.

- the composition according to the invention preferably contains less than 5% by weight, particularly preferably less than 3% by weight and very particularly preferably less than 1% by weight of water.

- the organic component of the composition according to the invention which is not included in components A, B, C and D, respectively, and which has a molecular weight of more than 800 g/mol (preferably more than 500 g/mol), preferably according to the invention a weight fraction of at most 35% by weight in total in the composition, particularly preferably a weight fraction of at most 8% by weight. Higher molecular weight components usually increase viscosity and thus increase operability. The molar mass of a component having a molecular weight of up to 800 g/mol (or up to 500 g/mol) is usually obtained by NMR taking into account the integration of the corresponding NMR-resonance signal. In a particularly preferred embodiment the composition is substantially free of such additional components having a molecular weight of greater than 800 g/mol (preferably greater than 500 g/mol).

In one embodiment of the invention, the composition according to the invention comprises

i) 30 to 90% by weight of an amide compound (A),

ii) from 8 to 55% by weight of the urea compound (B),

iii) 0 to 15% by weight of the ionogen compound (C) and

iv) from 2 to 25% by weight of an organic solvent (D)

contains

The presence of solvent (D) is in some cases practical and often alternatively the solvent is omitted. Thus, it is generally suitable when the mixture of the amide compound (A) and the urea compound (B) is provided (without D) in liquid or single-phase form (in some cases in the presence of the ionogen compound (C)).

A higher solvent fraction means that in order to obtain sufficiently high concentrations of the rheologically active ingredients (A) and (B) in the final application, undesirably higher amounts of the composition in question must be introduced into the application system.

Organic solvents are chosen by the person skilled in the art (especially sufficient inertness and rheology), especially taking into account their subsequent use as (rheological) additives. Corresponding solvents usually have a molecular weight of up to 250 g/mol. Since solvents are usually used, preference is given to using at most three, particularly preferably at most two, different solvents. Very particular preference is given to the use of no solvents at all or the use of at most one solvent.

In one preferred embodiment of the invention, the composition according to the invention comprises

(i) 40 to 85% by weight of the amide compound (A),

(ii) 15 to 60% by weight of the urea compound (B),

(iii) 0 to 5% by weight of the ionogen compound (C) and

(iv) 0 to 25% by weight of an organic solvent (D)

contains

Furthermore, each of A, B, C and D and said different components are preferably in the composition according to the invention in total in a fraction of 0 to 30% by weight, particularly preferably in a fraction of 0 to 20% by weight, very particularly Preferably in a fraction of 0 to 10% by weight, particularly preferably in a fraction of 0 to 5% by weight or in a fraction of 0 to 3% by weight.

In one particularly preferred embodiment of the invention, the composition according to the invention comprises

(i) 45 to 82% by weight of the amide compound (A),

(ii) 18 to 55% by weight of the urea compound (B),

(iii) 0 to 4% by weight of the ionogen compound (C) and

(iv) 0 to 10% by weight of an organic solvent (D)

contains

In one very general embodiment of the invention, the composition according to the invention comprises

(i) 50 to 75% by weight of the amide compound (A),

(ii) 25 to 50% by weight of the urea compound (B),

(iii) 0 to 3% by weight of the ionogen compound (C) and

(iv) 0 to 5% by weight of an organic solvent (D)

contains

It is furthermore particularly preferably in a fraction of 0 to 20% by weight, particularly preferably in a fraction of 0 to 10% by weight, in total in the composition according to the invention different from each of A, B, C and D, in the composition according to the invention preferably in a fraction of 0 to 5% by weight, particularly preferably in a fraction of 0 to 3% by weight.

In a preferred embodiment of the present invention, 50 to 100% by weight of the amide compound (A) does not have an amide group in which a hydrogen is bonded to a nitrogen atom, and 50 to 100% by weight of the amide compound (A) also includes Ra, Rb , Rc and Rd are represented by formula (I) wherein none of the residues are hydrogen.

Often 50 to 100% by weight of the amide compound (A) is represented by the following formula (Ia).

Not infrequently, 50 to 100% by weight of the amide compound (A) is represented by the formula (1a), wherein Ra and Rb and/or Rc and Rd represent an N-atom bonded to Ra and Rb and/or Rc and Rd and Together they form a branched or unbranched saturated or unsaturated ring having 4 to 7 ring atoms according to formula (ß-1) and having up to 2 heteroatoms selected from the group consisting of O and N.

The corresponding structure may schematically be as follows:

또는

or

R-Ring1 and R-Ring2 are generally present as bridged aliphatic moieties having 4 to 6 C-atoms, optionally including an ether group as a substituent.

The respective amide compounds (A) are prepared according to the structure type according to known organic chemistry methods. The preparation of this type of structure is expediently made via reaction with suitable amines starting from dicarboxylic acids or the corresponding higher functional carboxylic acids. As an alternative to the corresponding carboxylic acid, its reactive derivative (eg anhydride, halide or ester) can also be reacted with the corresponding amine for amidation. A possible synthetic route is to react the corresponding carboxylic acid with thionyl chloride to obtain the acid chloride (general conditions: 5 h at 60 °C, in some cases thionyl chloride is used in excess and distilled off after the reaction), without water It consists of dissolution in an organic solvent (such as toluene) which does not exist, and reaction therewith of an acid chloride with a suitable amine (general conditions: initiation of the reaction at 0° C. and warming to room temperature within 6 hours). Subsequent purification can be carried out, for example, by distillation.

The preparation of compounds of type (Ib) (see below) is preferably effected by the use of the corresponding cyclic amines, such as piperidine, pyrrolidine or morpholine. The preparation of the corresponding amides is disclosed, for example, in US 3,417,114. In addition, the preparation processes that can be used for the preparation of the acid amides of monocarboxylic acids are likewise dedicated to the preparation of the acid amides of dicarboxylic acids and of higher functional carboxylic acids: a corresponding preparation process is described for example in US 2,667,511 , US 3,288,794, US 3,751,465 or US 3,674,851.

In a further embodiment, 50 to 100% by weight of the amide compound (A) is represented by formula (1a) wherein each of Ra, Rb, Rc and/or Rd is not included in the ring.

According to another variant of the present invention, 50 to 100% by weight of the amide compound (A) of the formula (I) is represented by the following formula (Ib):

(Ib).

(Ib).

In certain embodiments, 50-100% by weight of formula (I) of amide compound (A) is represented by formula (lb) together form a branched or unbranched saturated or unsaturated ring having 5 to 7 ring atoms according to formula (γ-1) and having up to 2 heteroatoms selected from the group consisting of O and N.

In this case, preference is given to rings having 6 ring atoms, which are particularly preferably obtained by reaction of piperazine with the corresponding carboxylic acid (or a reaction derivative thereof):

In another embodiment, 50-100% by weight of the amide compound (A) of Formula (I) is represented by Formula (Ib), wherein Ra and Rb and/or Rc and Rd are, Ra and Rb and/or Rc and branched or unbranched saturated or unsaturated according to formula (α-1) and having 4 to 10 ring atoms and having up to 2 heteroatoms selected from the group consisting of O and N, together with the CO-N group bonding to Rd form a ring

Illustratively this is specified by the following two structures:

Often the Rz moiety is a C2- to C6-alkylene radical or a cyclohexylene radical or a xylylene radical (-CH ₂ -C ₆ H ₄ -CH ₂ -).

Often R-Ring3 and R-Ring4 exist as -(CH ₂ ) ₃ - and/or as -(CH ₂ ) ₄ -.

In particular, in general, R-Ring3 and R-Ring4 each exist as -(CH ₂ ) ₃ -.

The respective amide compounds (A) are prepared according to the structure type according to known organic chemistry methods. For example, alkylenediamines, arylenediamines and alkylarylenediamines or (poly)etherdiamines (where R has no further amino or amide groups) or the corresponding higher functional polyamines (wherein R represents further amino or amide groups) ) with the corresponding, optionally substituted carboxylic acids or their derivatives (eg halides, anhydrides, esters, and also lactones as special cases of esters). Other types of structures are preferably prepared by reaction of the corresponding diamine or polyamine with the corresponding lactone. Other types of preparation are disclosed, for example, in US 5,326,880, US 3,989,815 and US 6,497,886.

The rheological effect of the amide compound (A) is significantly increased by the presence of the urea compound (B).

Often from 70 to 100% by weight of the urea compound (B) has at least two urea groups or at least one urea group and at least one urethane group.

In one embodiment, 50 to 100% by weight of the urea compound (B) is in the form of the formula (II):

[Formula II]

In the above formula,

R ³¹ and R ³² are the same or different at each occurrence and, independently of one another at each occurrence, are branched or unbranched saturated or unsaturated organic radicals containing from 1 to 100 carbon atoms (in each case not more than 1 has a urea group and no more than one urethane group);

R ³³ and R ³⁴ are, at each occurrence, independently of one another, the same or different, in each case a branched or unbranched polyester radical containing from 1 to 300 carbon atoms and optionally an ether radical, from 2 to 300 branched or unbranched polyether radicals containing carbon atoms, branched or unbranched polyamide radicals containing 1 to 300 carbon atoms, polysiloxane radicals containing 3 to 100 silicon atoms, branched or unbranched a C ₂ -C ₂₂ alkylene radical, a branched or unbranched C ₃ -C ₁₈ alkenylene radical, a C ₅ -C ₁₂ arylene radical and/or a branched or unbranched C ₇ -C ₂₂ arylalkylene radical;

Z and W are the same or different at each occurrence and, independently of one another at each occurrence, are NH-CO-O and/or NH-CO-NH;

n is the same or different at each occurrence and is from 1 to 150, preferably from 2 to 120.

In a special embodiment of the invention, 50 to 100% by weight of the urea compound (B) have in each case a molar mass of 2,000 to 55,000 and 4 to 150 urea groups.

In a typical embodiment of the invention, 50 to 100% by weight of the urea compound (B) is present in each case in a form according to one formula selected from the group consisting of formulas IIIa, IIIb, IIIc and IIId:

[Formula IIIa]

[Formula IIIb]

[Formula IIIc]

[Formula IIId]

In the above formula,

AM, the same or different, is a linear or branched saturated or unsaturated aliphatic, aromatic or aliphatic-aromatic organic radical having 2 to 50 carbon atoms;

AM1 and AM2 at each occurrence are the same or different and, independently of one another in each case, are linear or branched saturated or unsaturated aliphatic, aromatic or aliphatic-aromatic organic radicals having from 1 to 50 carbon atoms;

IC1 and IC2 at each occurrence are the same or different, and in each case independently of one another are linear or branched saturated or unsaturated aliphatic, aromatic or aliphatic-aromatic hydrocarbon radicals having 2 to 40 carbon atoms;

IC3, identical or different, is a linear or branched saturated or unsaturated aliphatic, aromatic or aliphatic-aromatic hydrocarbon radical having 2 to 24 carbon atoms;

RP1 and RP2 in each case are the same or different and, in each case independently of one another, a linear or branched saturated or unsaturated aliphatic, aromatic or aliphatic-aromatic organic radical having 1 to 24 carbon atoms, and/or 1 a polyether radical having from to 120 ether oxygen atoms, and/or a polyester radical optionally containing ether groups and having from 1 to 100 ester groups, and/or a polyamide radical having from 1 to 100 amide groups, and/or polysiloxane radicals having 3 to 100 silicon atoms;

RP3 is the same or different and is a linear or branched saturated or unsaturated aliphatic, aromatic or aliphatic-aromatic hydrocarbon radical having from 2 to 24 carbon atoms, and/or a polyether radical having from 1 to 120 ether oxygen atoms, and / or polyamide radicals having 1 to 100 amide groups, and / or polysiloxane radicals having 3 to 100 silicon atoms, and / or polyester radicals optionally containing ether groups and having 1 to 100 ester groups;

p is the same or different and is 0 and/or 1.

Here, preferably 70 to 100% by weight of the urea compound (B) has in each case one formula selected from the group consisting of formulas IIIa, IIIb, IIIc and IIId;

AM is the same or different,

(CH ₂ ) _q

is selected from the group consisting of;

R _x and R _y are the same or different and at each occurrence are independently CH ₃ and/or hydrogen;

q is the same or different and is an integer from 2 to 12;

AM1 and AM2 are the same or different in each case and represent n-propyl, isopropyl, butyl, isobutyl, tert-butyl, lauryl, oleyl, stearyl, polyisobutylene, 2 to 40 ether oxygen atoms polyether, benzyl, methylbenzyl, cyclohexyl, carboxyalkyl, hydroxyalkyl and alkylalkoxysilane having;

IC1 and IC2 are the same or different in each case,

is selected from the group consisting of;

IC3 is the same or different and is selected from the group consisting of methyl, ethyl, phenyl, benzyl, cyclohexyl and stearyl;

RP1 and RP2 are the same or different in each case and represent structural units of branched or unbranched C ₁ -C ₁₈ alkyl, oleyl, benzyl, allyl, preferably ethylene oxide, propylene oxide and/or butylene oxide polyether radicals containing, and polyester radicals containing structural units of ε-caprolactone and/or δ-valerolactone;

RP3 is the same or different, linear or branched C ₁ -C ₁₈ alkyl, linear or branched C ₂ -C ₁₈ It is selected from the group consisting of polyethers containing structural units of alkenyl, preferably ethylene oxide, propylene oxide and/or butylene oxide, and having 1 to 25 ether oxygen atoms.

In a particular embodiment, 70 to 100% by weight of the urea compound (B) is prepared by reacting isocyanates oligomerized by isocyanurate and/or uretdione formation in each case with monofunctional amines.

In a particular embodiment of the invention, 95 to 100% by weight, preferably 98 to 100% by weight, of the urea compound (B) contain in each case at least one moiety of the formula (IVa), does not contain the molecular part of:

[Formula IVa]

[Formula IVb]

In the above formula,

Y ₁ is the same or different and is a branched or unbranched saturated or unsaturated hydrocarbon radical containing 6 to 20 carbon atoms;

Y ₂ is the same or different and is a branched or unbranched saturated or unsaturated hydrocarbon radical containing 6 to 20 carbon atoms.

The preparation of the urea compound (B) can be carried out in a known manner by reacting the corresponding isocyanate with an amine. The method for preparing such a urea compound is, for example, in European Patent Nos. 0 006 252, German Patent Nos. 2822908, 10241853, 19919482 and 1188779, and German Patent Publication No. 10 2008 059702 in more detail. has been described. The preparation of polyurea compounds of particularly higher molar mass is described, for example, in EP 2 292 675 .

In one embodiment of the invention, the composition according to the invention contains the ionogen compound (C). It is present mostly in the form of a salt, preferably as a lithium-, calcium- or magnesium salt, particularly preferably as a lithium- or calcium salt. The anion (counterion) is preferably halide, pseudohalide, formate, acetate and/or nitrate, particularly preferably chloride, acetate and/or nitrate. In the meaning of the present invention, so-called ionic liquids that are not organic solvents are also included in the ionogen compound (C).

In one embodiment of the invention the composition according to the invention contains 0.5 to 4.0% by weight of the ionogen compound (C), wherein 50 to 100% by weight of the ionogen compound (C) is a lithium- or calcium salt, It is preferably present as its chloride, acetate and/or nitrate salt.

The composition according to the invention is suitable for preferably rheological control, in particular thixotropy, of liquid systems or liquid mixtures.

This liquid mixture is preferably used as a coating, in particular as a paint or varnish, as a plastic formulation, as a pigment paste, as a sealing agent, as a cosmetic, as a ceramic formulation, as an adhesive formulation, as a casting compound, as a building material formulation, as a lubricant, It exists as a filling compound, as a printing ink or as a liquid ink (eg as an inkjet ink). A further use is possible as an auxiliaries for reducing or preventing migration in the spray process (so-called "drift reduction/deposition aids").

The composition according to the invention is suitable for rheological control of liquid mixtures, in particular for thixotropic properties.

The present invention also relates to the use of the composition according to the invention for regulating the rheology of liquid mixtures, in particular for thixotropy.

The liquid mixture can be used as a coating, in particular as a paint or varnish, as a plastics formulation, as a pigment paste, as a sealing agent, as a cosmetic, as a ceramic formulation, as an adhesive formulation, as a casting compound, as a drilling fluid, as a building material formulation, as a lubricant , as a filling compound, as a printing ink or as a liquid ink.

Finally, the present invention provides a formulation to which 0.1 to 7.5% by weight of the composition according to the present invention is added, such as paints, plastic formulations, pigment pastes, sealant formulations, cosmetics, ceramic formulations, adhesive formulations, potting compositions, construction material formulations , lubricants, putties, inks for printers or formulations present as inks.

As a rheology modulating substance, preferably a thixotropic agent, for modulating the rheology of paints, printing inks, inks (eg inkjet inks), plastic formulations, cosmetic formulations, construction material formulations, lubricants and/or adhesives. Particular preference is given to the use of the composition according to the invention.

Paints, printer inks and (inkjet) inks may be solvent-based, solvent-free or water-based paints, printer inks and inkjet inks. Paints are used in a wide variety of areas of application, such as automotive paints, construction paints, protective paints (e.g. painting of ships and bridges), can and coil paints, wood and furniture paints, industrial paints, plastic paints, wire paints, food and seed materials. It can be used in the area of coatings, and so-called Color Resists (eg used in color filters in LC displays). The application areas of the paint are also usually paste-like substances having a very high solid fraction and a low liquid component fraction, such as so-called pigment pastes, or finely divided metal particles or metal powders (eg silver, copper, zinc, aluminum, bronze). , brass) based paste.

The plastic formulation may preferably be a (liquid) starting material for making plastics that are converted by a chemical crosslinking process (“curing” to a duromer). Accordingly, preferred plastic formulations are unsaturated polyester resins, vinyl ester resins, acrylate resins, epoxy resins, polyurethane resins, formaldehyde resins (eg, melamine-formaldehyde or urea-formaldehyde). They will be cured under a wide variety of conditions, for example at room temperature (low temperature curing systems) or at high temperatures (high temperature curing systems), optionally or under the application of pressure (“closed mold” application, sheet molding compounds or bulk molding compounds). can Preferred plastic formulations also include PVC plastisols.

Cosmetic preparations are so-called personal care or health care areas, for example lotions, creams, pastes (eg toothpaste), foams (eg shaving foams), gels (eg shaving gels, shower gels, medicinally active ingredients in gel formulations) , hair shampoo, liquid soap, nail paint, lipstick, and various liquid compositions used in hair dye.

Construction material formulations are liquid or paste-like when processed and may include substances used in construction applications and solidifying after curing, for example, hydraulic binders such as concrete, cement, mortar, tile adhesives, gypsum.

Lubricants are agents used for lubrication, such as reducing friction and abrasion, and for power transmission, cooling, vibration damping, and rod and corrosion protection, with liquid lubricants and lubricating greases being preferred. Antifriction agents and drilling fluids (eg, those used in petroleum production) are also included in the definition of lubricants.

The adhesive can be any liquid under the conditions of the process material to which the parts to be joined can be joined by means of surface adhesion and internal strength. Adhesives may be solvent-based, solvent-free or water-based.

Hereinafter, the present invention will be described in more detail based on examples.

In the examples below, the amine number was measured according to DIN 16945. Similarly, the OH number was determined according to DIN/ISO 4629.

The following commercially available raw materials were used:

Example 1b:

412.5 g (2.48 mol) of hexamethylene diamine in the form of a 70% aqueous solution was placed in a reaction vessel (round bottom flask equipped with a stirrer, reflux condenser, water separator and dropping funnel) at 60° C. under a nitrogen atmosphere. 430.0 g (5.0 mol) of butyrolactone was added dropwise within 60 minutes under stirring. The temperature was raised to 90°C due to the exothermic reaction. Then 0.4 g of p-toluenesulfonic acid was added.

After that, the temperature was raised to 170°C by a temperature gradient of about 10°C for 20 minutes. It was then heated to a final temperature of 250° C. and held for 18.5 hours. The reaction water was removed from the reaction mixture by distillation during the entire reaction time. The reaction product is a yellow, slightly viscous liquid with an amine number of 15.4 mg KOH/g.

For removal of residual reactants, the reaction product was purified by distillation using a thin film evaporator at 120° C. and less than 1 mbar. Thereafter, the amine titer was less than 1 mg KOH/g.

Example 2b:

Into a reaction vessel (round bottom flask equipped with a stirrer, reflux condenser, water separator and dropping funnel) was placed 42.0 g (0.7 mol) of ethylene diamine at 60° C. under a nitrogen atmosphere. 132.6 g (1.54 mol) of butyrolactone was added dropwise within 45 minutes under stirring. The temperature was raised to 140°C due to the exothermic reaction.

After that, the temperature was raised to 250°C by a temperature gradient of about 10°C for 45 minutes. This final temperature was maintained for 9 hours. The reaction water was removed from the reaction mixture by distillation during the entire reaction time. The final product is crystalline.

Example 3b:

Into a reaction vessel (round bottom flask equipped with a stirrer, reflux condenser, water separator and dropping funnel) was placed 74.1 g (1.0 mol) of 1,3-propanediamine at 60° C. under a nitrogen atmosphere. 189.4 g (2.2 mol) of butyrolactone were added dropwise within 75 minutes under stirring. The temperature was raised to 120°C due to the exothermic reaction. Then 0.4 g of p-toluenesulfonic acid was added.

After that, the temperature was raised to 250°C by a temperature gradient of about 10°C for 45 minutes. This final temperature was maintained for 9 hours. The reaction water was removed from the reaction mixture by distillation during the entire reaction time. The reaction product had a hydroxyl number of 4.0.

Example 4b:

Into a reaction vessel (round bottom flask equipped with a stirrer, reflux condenser, water separator and dropping funnel) was placed 37.1 g (0.5 mol) of 1,2-propane diamine at 60° C. under a nitrogen atmosphere. 94.7 g (1.1 mol) of butyrolactone was added dropwise within 40 minutes under stirring. The temperature was raised to 110°C due to the exothermic reaction.

After that, the temperature was raised to 250°C by a temperature gradient of about 10°C for 45 minutes. This final temperature was maintained for 9 hours. The reaction water was removed from the reaction mixture by distillation during the entire reaction time. The final product is crystalline.

Example 5b:

Into a reaction vessel (round bottom flask equipped with a stirrer, reflux condenser, moisture separator and dropping funnel) was placed 64.9 g (0.73 mol) of 1,4-diaminobutane at 60° C. under a nitrogen atmosphere. 69.7 g (0.81 mol) of butyrolactone was added dropwise within 30 minutes under stirring. The temperature was raised to 100°C due to the exothermic reaction.

After that, the temperature was raised to 250°C by a temperature gradient of about 10°C for 45 minutes. This final temperature was maintained for 9 hours. The reaction water was removed from the reaction mixture by distillation during the entire reaction time. The final product is crystalline.

Example 6b:

Into a reaction vessel (round bottom flask equipped with a stirrer, reflux condenser, moisture separator and dropping funnel) was placed 72.1 g (0.5 mol) of molten 1,8-octamethylenediamine at 100° C. under a nitrogen atmosphere. 94.7 g (1.1 mol) of butyrolactone was added dropwise within 20 minutes under stirring. The temperature was raised to 160°C due to the exothermic reaction.

After that, the temperature was raised to 250°C by a temperature gradient of about 10°C for 45 minutes. This final temperature was maintained for 12 hours. The reaction water was removed from the reaction mixture by distillation during the entire reaction time. The final product is liquid.

Example 7b:

Into a reaction vessel (round bottom flask equipped with a stirrer, reflux condenser, moisture separator and dropping funnel) was placed 84.1 g (0.42 mol) of molten dodecanediamine at 80° C. under a nitrogen atmosphere. 79.5 g (0.92 mol) of butyrolactone was added dropwise within 20 minutes under stirring. The temperature was raised to 135°C due to the exothermic reaction.

After that, the temperature was raised to 250°C by a temperature gradient of about 10°C for 20 minutes. This final temperature was maintained for 11 hours. 0.4 g of p-toluenesulfonic acid was added. The reaction water was removed from the reaction mixture by distillation during the entire reaction time. The final product is liquid. It is a bright red solid.

Example 8b:

68.1 g (0.5 mol) of m-xylylenediamine was placed in a reaction vessel (round bottom flask equipped with a stirrer, reflux condenser, moisture separator and dropping funnel) at 30° C. under a nitrogen atmosphere. 94.1 g (1.1 mol) of butyrolactone were added dropwise within 10 minutes under stirring. The mixture was first heated to 100° C. and then raised in temperature by a temperature gradient of about 10° C. for 20 minutes. An exothermic reaction was confirmed at 120 °C. The temperature rose to 170°C. Thereafter, the temperature was raised to 250° C. by a temperature gradient of about 10° C. for 20 minutes and maintained for 7 hours. 0.4 g of p-toluenesulfonic acid was added and the mixture was stirred at 250° C. for another 6 hours.

The reaction water was removed from the reaction mixture by distillation during the entire reaction time. The reaction product is a highly viscous orange liquid with an amine number of 0.6 mg KOH/g.

Example 9b:

Into a reaction vessel (round bottom flask equipped with a stirrer, reflux condenser, moisture separator and dropping funnel) was placed 57.1 g (0.5 mol) of 1,2-diaminocyclohexane at 30° C. under a nitrogen atmosphere. 94.1 g (1.1 mol) of butyrolactone were added dropwise within 10 minutes under stirring. The temperature was raised by a temperature gradient of about 10° C. for 20 minutes. An exothermic reaction was confirmed at 90 °C. The temperature rose to 104°C. Thereafter, the temperature was raised to 250° C. by a temperature gradient of about 10° C. for 20 minutes and maintained for 6 hours. 0.4 g of p-toluenesulfonic acid was added and the mixture was stirred at 250° C. for another 6 hours. The reaction water was removed from the reaction mixture by distillation during the entire reaction time. The final product is a solid.

Example 10b:

Into a reaction vessel (round bottom flask equipped with a stirrer, reflux condenser, moisture separator and dropping funnel) was placed 68.1 g (0.4 mol) of isophoronediamine at 30° C. under a nitrogen atmosphere. 75.8 g (0.88 mol) of butyrolactone was added dropwise within 10 minutes under stirring. The mixture was first heated to 100° C. and then raised in temperature by a temperature gradient of about 10° C. for 20 minutes. An exothermic reaction was confirmed at 120 °C. The temperature rose to 160°C. Thereafter, the temperature was raised to 250° C. by a temperature gradient of about 10° C. for 20 minutes and maintained for 6 hours. 0.4 g of p-toluenesulfonic acid was added and the mixture was stirred at 250° C. for another 6 hours.

The reaction water was removed from the reaction mixture by distillation during the entire reaction time. The reaction product is a liquid with an amine number of 15.6 mg KOH/g.

Example 11b:

92.0 g (0.4 mol) of polyetherdiamine (Jeffamine D230 from Huntsman) was placed in a reaction vessel (round bottom flask equipped with a stirrer, reflux condenser, water separator and dropping funnel) at 30° C. under a nitrogen atmosphere. 75.8 g (0.88 mol) of butyrolactone was added dropwise within 10 minutes under stirring. The temperature was raised to 250° C. by a temperature gradient of about 10° C. in 20 minutes and held at this temperature for 6 hours. 0.4 g of p-toluenesulfonic acid was added and the mixture was stirred at 250° C. for another 6 hours.

The reaction water was removed from the reaction mixture by distillation during the entire reaction time. The final product is a slightly viscous liquid with an amine number of 6 mg KOH/g.

Example 12b:

120.0 g (0.3 mol) of polyetherdiamine (Jeffamine D400 from Huntsman) was placed in a reaction vessel (round bottom flask equipped with a stirrer, reflux condenser, moisture separator and dropping funnel) at 30° C. under nitrogen atmosphere. 56.8 g (0.66 mol) of butyrolactone was added dropwise within 10 minutes under stirring. The temperature was raised to 250° C. by a temperature gradient of about 10° C. in 20 minutes and held at this temperature for 6 hours. 0.4 g of p-toluenesulfonic acid was added and the mixture was stirred at 250° C. for another 6 hours. The reaction water was removed from the reaction mixture by distillation during the entire reaction time. The final product is a slightly viscous liquid with an amine number of 7.7 mg KOH/g.

Example 13b:

200.0 g (0.1 mol) of polyetherdiamine (Jeffamine D2000 from Huntsman) was placed in a reaction vessel (round bottom flask equipped with a stirrer, reflux condenser, water separator and dropping funnel) at 80° C. under nitrogen atmosphere. 18.9 g (0.22 mol) of butyrolactone was added dropwise within 10 minutes under stirring. The temperature was raised to 200° C. by a temperature gradient of about 10° C. in 20 minutes and held at this temperature for 6 hours. 0.4 g of p-toluenesulfonic acid was added and the mixture was stirred at 250° C. for another 6 hours. The reaction water was removed from the reaction mixture by distillation during the entire reaction time. The final product is a viscous liquid with an amine number of 6.5 mg KOH/g.

Example 14b:

81.7 g (0.39 mol) of 4,9-dioxadecane-1,2-diamine was placed in a reaction vessel (round bottom flask equipped with a stirrer, reflux condenser, moisture separator and dropping funnel) at 80° C. under a nitrogen atmosphere. 75.7 g (0.87 mol) of butyrolactone was added dropwise within 10 minutes under stirring. The temperature was raised to 200° C. by a temperature gradient of about 10° C. in 20 minutes and held at this temperature for 6 hours. 0.4 g of p-toluenesulfonic acid was added and the mixture was stirred at 250° C. for another 6 hours. The reaction water was removed from the reaction mixture by distillation during the entire reaction time. The final product is a slightly viscous liquid with an amine number of 3.5 mg KOH/g.

Example 15b:

Into a reaction vessel (round bottom flask equipped with a stirrer, dropping funnel and reflux condenser) were placed 315.0 g (1.9 mol) of glutaric acid dimethyl ester and 508.0 g (3.8 mol) of dibutylamine under a nitrogen atmosphere. The reaction mixture was stirred at 100° C. for 2 hours. A moisture separator was then connected to the apparatus and the temperature was raised to 170°C. At this time, 200 g of methanol was isolated. After the reaction time was over, the reaction mixture had an amine value of 73 mg KOH/g.

For separation of the remaining reactants, the reaction product was purified by distillation using a thin film evaporator at 120° C. and less than 1 mbar. After that, the amine value was 4.5 mg KOH/g.

Example 16b:

In a four-necked flask equipped with a stirrer, thermometer and water separator, 84.0 g of pentanoic acid-5-(dimethylamino)-2-methyl-5-oxo-methylester (0.449 mol) and 116.0 g of dibutylamine (0.898 mol) ) is warmed to 150° C. under stirring. The produced methanol is separated in a water separator. The mixture is heated at this temperature for 16 hours. Then, it was warmed to 170° C. and a vacuum of 0.8 mbar was applied for 2 hours to remove volatile components. The resulting clear liquid product is controlled by IR-spectroscopy in the absence of an ester band at 1711 cm ^-1 : no ester band was detected. Yield: 119 g of clear liquid (=93% of theoretical yield).

Example 17b:

In a four-necked flask equipped with a stirrer, thermometer and water separator, 90.8 g of pentanoic acid-5-(dimethylamino)-2-methyl-5-oxo-methylester (0.485 mol) and 130.0 g of oleylamine (0.482 mol) ) is warmed to 150° C. under stirring. The produced methanol is separated in a water separator. The mixture is heated at this temperature for 10 hours. Then, it is cooled to 80° C. and a vacuum of 0.8 mbar is applied at this temperature for 2 hours to remove residual volatile components. The resulting clear liquid product is controlled by IR-spectroscopy in the absence of an ester band at 1711 cm ^-1 : no ester band was detected. Yield: 198 g of clear pasty liquid (=97% of theoretical yield).

Example 18t:

140.8 g of pentanoic acid-5-(dimethylamino)-2-methyl-5-oxo-methylester (0.752 mol) and 43.7 g of 1,6 in a four-necked flask equipped with a stirrer, dropping funnel, thermometer and water separator -Hexamethylenediamine (0.376 mol) is warmed to 180°C under stirring. The produced methanol is separated in a water separator. The mixture is heated at this temperature for 10 hours. Then, it is cooled to 150° C. and a vacuum of 0.8 mbar is applied at this temperature for 2 hours to remove residual volatile components.

The resulting clear liquid product is controlled by IR-spectroscopy in the absence of an ester band at 1711 cm ^-1 : no ester band was detected. Yield: 150 g of viscous clear liquid (=94% of theoretical yield).

Example 19t:

150.3 g of pentanoic acid-5-(dimethylamino)-2-methyl-5-oxo-methylester (0.803 mol) and 54.6 g of meta-k in a four-necked flask equipped with a stirrer, dropping funnel, thermometer and water separator Silylenediamine (0.402 mol) is warmed to 150° C. under stirring. The produced methanol is separated in a water separator. The mixture is heated at this temperature for 11 hours. Then, it is cooled to 150° C. and a vacuum of 0.8 mbar is applied at this temperature for 2 hours to remove residual volatile components. The resulting clear liquid product is controlled by IR-spectroscopy in the absence of an ester band at 1711 cm ^-1 : no ester band was detected.

Example 20p:

160.2 g of pentanoic acid-5-(dimethylamino)-2-methyl-5-oxo-methylester (0.856 mol) and 44.2 g of diethylenetri in a four-necked flask equipped with a stirrer, dropping funnel, thermometer and water separator The amine (0.428 mol) is warmed to 180° C. with stirring. The produced methanol is separated in a water separator. The mixture is heated at this temperature for 15 hours. Then, it is cooled to 150° C. and a vacuum of 0.8 mbar is applied at this temperature for 2 hours to remove residual volatile components. The resulting clear liquid product is controlled by IR-spectroscopy in the absence of an ester band at 1711 cm ^-1 : no ester band was detected. Yield: 168 g of solid product (=95% of theoretical yield).

After completion of the reaction, the reaction water produced was distilled on a rotary evaporator. A light yellow liquid with an amine number of 4 mg KOH/g was obtained.

Composition K1:

Step 1

First, 64.4 g of a diisocyanate-monoadduct according to patent document EP 1188779 was prepared with polyethylene glycol monobutyl ether having a hydroxyl value of 220 mg KOH/g (measured according to DIN / ISO 4629) and 35% of 2,4-toluylene diisocyanate and 65% of 2,6-toluylene diisocyanate.

Step 2

Prepare a four-necked flask equipped with a stirrer, dropping funnel, thermometer and reflux condenser. Add 118.2 g of the reaction product from Example 1b and warm to 120° C. under stirring under nitrogen atmosphere. 4.2 g of lithium chloride are added and dissolved under stirring at this temperature for 1 hour. The temperature is then lowered to 80°C. Add 10.2 g of m-xylylenediamine and homogenize the mixture.

The isocyanate adduct prepared previously (step 1) is slowly added dropwise to the amine solution under stirring so that the temperature does not exceed 85° C. within 1 hour. The reaction mixture is stirred at 80° C. for another 3 hours to complete the reaction. The amine number is 3.6 mg KOH/g (determined according to DIN 16945). The product is a highly viscous liquid and contains 38% by weight of the urea compound.

Composition K2:

Step 1

First, 64.4 g of a diisocyanate-monoadduct according to patent document EP 1188779 was mixed with polyethylene glycol monobutyl ether having a hydroxyl value of 220 mg KOH/g (measured according to DIN / ISO 4629) and 35% of 2, Prepared from a mixture of 4-toluylenediisocyanate and 65% 2,6-toluylenediisocyanate.

Step 2

Prepare a four-necked flask equipped with a stirrer, dropping funnel, thermometer and reflux condenser. Add 188 g of the reaction product from Example 8b and warm to 120° C. under stirring under nitrogen atmosphere. Add 5.1 g of lithium chloride and dissolve under stirring at this temperature for 1 hour. The temperature is then lowered to 80°C. Add 10.2 g of m-xylylenediamine and homogenize the mixture.

The isocyanate adduct prepared previously (step 1) is slowly added dropwise to the amine solution under stirring so that the temperature does not exceed 85° C. within 1 hour. The reaction mixture is stirred at 80° C. for another 3 hours to complete the reaction. A cloudy, colorless, low-viscosity product is obtained. The amine titer is 3 mg KOH/g (determined according to DIN 16945). The product contains 28% by weight of the urea compound.

Composition K3:

Step 1

First, 64.4 g of a single adduct according to Patent Document EP 1188779 was prepared with polyethylene glycol monomethyl ether having a molar mass of 450 g/mol and 35% of 2,4-toluylene diisocyanate and 65% of 2,6- Prepared from a mixture of toluylenediisocyanates.

Step 2

In a four neck flask equipped with a stirrer, dropping funnel, thermometer and reflux condenser, 187.8 g of the reaction product from example 7b is placed, warmed to 100° C. and when this temperature is reached, 5.9 g of lithium chloride are added. The lithium chloride is then dissolved under stirring at 100° C. within 1 hour. The temperature is then lowered to 80°C.

Add 10.2 g of m-xylylenediamine and homogenize the mixture. The isocyanate adduct prepared previously (step 1) is slowly added dropwise to the amine solution under stirring so that the temperature does not exceed 85° C. within 1 hour. The reaction mixture is stirred at 80° C. for 3 hours to complete the reaction. A slightly brownish waxy product is obtained, which is liquid at 80°C. The product contains 28% by weight of the urea compound.

Composition K4:

Step 1

First, 64.4 g of a single adduct according to Patent Document EP 1188779 was prepared with polyethylene glycol monomethyl ether having a molar mass of 450 g/mol and 35% of 2,4-toluylene diisocyanate and 65% of 2,6- Prepared from a mixture of toluylenediisocyanates.

Step 2

Into a four-necked flask equipped with stirrer, dropping funnel, thermometer and reflux condenser, 187.8 g of the reaction product from example 11b are placed, warmed to 100° C. and when this temperature is reached, 4.2 g of lithium chloride are added. The lithium chloride is then dissolved under stirring at 100° C. within 1 hour. The temperature is then lowered to 80°C.

Add 10.2 g of m-xylylenediamine and homogenize the mixture. The previously prepared isocyanate adduct (step 1) is slowly added dropwise to the amine solution under stirring so that the temperature does not exceed 85° C. within 1 hour. The reaction mixture is stirred at 80° C. for 3 hours to complete the reaction. A cloudy viscous product is obtained. The product contains 28% by weight of the urea compound.

Composition K5:

Step 1

First, 64.4 g of a diisocyanate-monoadduct according to patent document EP 1188779 was mixed with polyethylene glycol monobutyl ether having a hydroxyl value of 220 mg KOH/g (measured according to DIN / ISO 4629) and 35% of 2, Prepared from a mixture of 4-toluylenediisocyanate and 65% 2,6-toluylenediisocyanate.

Step 2

Prepare a four-necked flask equipped with a stirrer, dropping funnel, thermometer and reflux condenser. Add 239.1 g of the mixture of reaction product from Example 15b and warm to 120° C. under stirring under nitrogen atmosphere. Add 5.1 g of lithium chloride and dissolve under stirring at this temperature for 1 hour. The temperature is then lowered to 80°C. Add 10.2 g of m-xylylenediamine and homogenize the mixture.

The isocyanate adduct prepared previously (step 1) is slowly added dropwise to the amine solution under stirring so that the temperature does not exceed 85° C. within 1 hour. The reaction mixture is stirred at 80° C. for another 3 hours to complete the reaction. A cloudy viscous product is obtained. The product contains 23% by weight of the urea compound.

Composition K6:

Step 1

First, 64.4 g of a diisocyanate-monoadduct according to patent document EP 1188779 was mixed with polyethylene glycol monobutyl ether having a hydroxyl value of 220 mg KOH/g (measured according to DIN / ISO 4629) and 35% of 2, Prepared from a mixture of 4-toluylenediisocyanate and 65% 2,6-toluylenediisocyanate.

Step 2

Prepare a four-necked flask equipped with a stirrer, dropping funnel, thermometer and reflux condenser. Add 31.2 g of the reaction product from Example 14b and warm to 120° C. under stirring under nitrogen atmosphere. 0.7 g of lithium chloride are added and dissolved at this temperature for 1 hour under stirring. The temperature is then lowered to 80°C. 3.0 g of m-xylylenediamine are added and the mixture is homogenized.

17.1 g of the isocyanate adduct prepared in step 1 is slowly added dropwise to the amine solution under stirring so that the temperature does not exceed 85° C. within 1 hour. The reaction mixture is stirred at 80° C. for another 3 hours to complete the reaction. The product contains 39% by weight of the urea compound.

Composition K7:

Step 1

First, a monoadduct according to patent document EP 1188779 is prepared from 2,4-toluylenediisocyanate (Desmodur T100, Bayer) and 1-dodecanol.

Step 2

In a reaction vessel (round bottom flask equipped with a stirrer, reflux condenser and dropping funnel) 12.6 g (0.3 mol) of LiCl is dissolved in 280 g of the reaction product of Example 1b with stirring under nitrogen atmosphere. Then 13.6 g (0.125 mol) of meta-xylylenediamine are added and the clear mixture is warmed to 80°C. Then 72.0 g (0.20 mol) of the above-mentioned isocyanate adduct (step 1) is added dropwise under stirring so that the temperature does not exceed 85° C. within 1 hour. The reaction mixture is stirred at 80° C. for 3 hours to complete the reaction. A clear viscous product is obtained. The fraction of the urea compound in the obtained product is 23% by weight.

Composition K8:

Step 1

First, 93.6 g of a single adduct according to patent document EP 1188779 was prepared by mixing polyethylene glycol monomethyl ether having a molar mass of 450 g/mol and 35% of 2,4-toluylene diisocyanate and 65% of 2,6- Prepared from a mixture of toluylenediisocyanates.

Step 2

In a four neck flask equipped with stirrer, dropping funnel, thermometer and reflux condenser, 162.0 g of the reaction product from Example 1b is placed, warmed to 100° C. and when this temperature is reached, 4.2 g of lithium chloride are added. The lithium chloride is then dissolved under stirring at 100° C. within 1 hour. The temperature is then lowered to 80°C.

Add 10.2 g of m-xylylenediamine and homogenize the mixture. The previously prepared isocyanate adduct (step 1) is slowly added dropwise to the amine solution under stirring so that the temperature does not exceed 85° C. within 1 hour. The reaction mixture is stirred at 80° C. for 3 hours to complete the reaction. A viscous, slightly brownish product is obtained. The product contains 38% by weight of the urea compound.

Composition K9:

Step 1

First, 93.6 g of a single adduct according to patent document EP 1188779 was prepared by mixing polyethylene glycol monomethyl ether having a molar mass of 450 g/mol and 35% of 2,4-toluylene diisocyanate and 65% of 2,6- Prepared from a mixture of toluylenediisocyanates.

Step 2

252.0 g of the reaction product from Example 14b is placed in a four-necked flask equipped with stirrer, dropping funnel, thermometer and reflux condenser, warmed to 100° C. and when this temperature is reached, 4.2 g of lithium chloride are added. The lithium chloride is then dissolved under stirring at 100° C. within 1 hour. The temperature is then lowered to 80°C.

Add 10.2 g of m-xylylenediamine and homogenize the mixture. The previously prepared isocyanate adduct (step 1) is slowly added dropwise to the amine solution under stirring so that the temperature does not exceed 85° C. within 1 hour. The reaction mixture is stirred at 80° C. for 3 hours to complete the reaction. A turbid, slightly brownish product is obtained. The amine titer is 3 mg KOH/g (determined according to DIN 16945). The product contains 29% by weight of the urea compound.

Composition K10:

Step 1

First, 93.6 g of a single adduct according to patent document EP 1188779 was prepared by mixing polyethylene glycol monomethyl ether having a molar mass of 450 g/mol and 35% of 2,4-toluylene diisocyanate and 65% of 2,6- Prepared from a mixture of toluylenediisocyanates.

Step 2

324.0 g of the reaction product from Example 16b are placed in a four-necked flask equipped with stirrer, dropping funnel, thermometer and reflux condenser, warmed to 100° C. and when this temperature is reached, 4.2 g of lithium chloride are added. The lithium chloride is then dissolved under stirring at 100° C. within 1 hour. The temperature is then lowered to 80°C.

Add 10.2 g of m-xylylenediamine and homogenize the mixture. The previously prepared isocyanate adduct (step 1) is slowly added dropwise to the amine solution under stirring so that the temperature does not exceed 85° C. within 1 hour. The reaction mixture is stirred at 80° C. for 3 hours to complete the reaction. A slightly brownish product is obtained. The product contains 24% by weight of the urea compound.

Comparative Example (not according to the invention)

Comparative Example V1:

Step 1

First, 64.4 g of a diisocyanate-monoadduct according to patent document EP 1188779 was mixed with polyethylene glycol monobutyl ether having a hydroxyl value of 220 mg KOH/g (measured according to DIN / ISO 4629) and 35% of 2, Prepared from a mixture of 4-toluylenediisocyanate and 65% 2,6-toluylenediisocyanate.

Step 2

Prepare a four-necked flask equipped with a stirrer, dropping funnel, thermometer and reflux condenser. 72.7 g of 1-ethylpyrrolidin-2-one was added, and the mixture was heated to 120° C. under stirring under nitrogen atmosphere. 4.2 g of lithium chloride are added and dissolved under stirring at this temperature for 1 hour. The temperature is then lowered to 80°C. Add 10.2 g of m-xylylenediamine and homogenize the mixture.

The isocyanate adduct prepared previously (step 1) is slowly added dropwise to the amine solution under stirring so that the temperature does not exceed 85° C. within 1 hour. The reaction mixture is stirred at 80° C. for another 3 hours to complete the reaction. A clear yellow product is obtained. The amine titer is 1 mg KOH/g (determined according to DIN 16945). The product contains 49% by weight of the urea compound.

Comparative Example V2:

Step 1

First, 64.4 g of a diisocyanate-monoadduct according to patent document EP 1188779 was mixed with polyethylene glycol monobutyl ether having a hydroxyl value of 220 mg KOH/g (measured according to DIN / ISO 4629) and 35% of 2, Prepared from a mixture of 4-toluylenediisocyanate and 65% 2,6-toluylenediisocyanate.

Step 2

Prepare a four-necked flask equipped with a stirrer, dropping funnel, thermometer and reflux condenser. 72.7 g of dimethyl sulfoxide was added, and the mixture was heated to 120° C. under stirring under a nitrogen atmosphere. 4.2 g of lithium chloride are added and dissolved under stirring at this temperature for 1 hour. The temperature is then lowered to 80°C. Add 10.2 g of m-xylylenediamine and homogenize the mixture.

The isocyanate adduct prepared previously (step 1) is slowly added dropwise to the amine solution under stirring so that the temperature does not exceed 85° C. within 1 hour. The reaction mixture is stirred at 80° C. for another 3 hours to complete the reaction. A clear yellow product is obtained. The amine titer is 1 mg KOH/g (determined according to DIN 16945). The product contains 49% by weight of the urea compound.

Comparative Example V3:

Step 1

First, 64.4 g of a diisocyanate-monoadduct according to patent document EP 1188779 was mixed with polyethylene glycol monobutyl ether having a hydroxyl value of 220 mg KOH/g (measured according to DIN / ISO 4629) and 35% of 2, Prepared from a mixture of 4-toluylenediisocyanate and 65% 2,6-toluylenediisocyanate.

Step 2

Prepare a four-necked flask equipped with a stirrer, dropping funnel, thermometer and reflux condenser. 72.7 g of N-methylpyrrolidone was added, and the mixture was heated to 120° C. under stirring under a nitrogen atmosphere. 4.2 g of lithium chloride are added and dissolved under stirring at this temperature for 1 hour. The temperature is then lowered to 80°C. Add 10.2 g of m-xylylenediamine and homogenize the mixture.

The isocyanate adduct prepared previously (step 1) is slowly added dropwise to the amine solution under stirring so that the temperature does not exceed 85° C. within 1 hour. The reaction mixture is stirred at 80° C. for another 3 hours to complete the reaction. A clear yellow product is obtained. The product contains 49% by weight of the urea compound.

Comparative Example V4:

First, a single adduct according to patent document EP 1188779 is prepared from 2,4-toluylene diisocyanate (Desmodur T100, Bayer) and lauryl alcohol.

In a reaction vessel (round bottom flask equipped with a stirrer, reflux condenser and dropping funnel), 1.7 g (0.039 mol) of LiCl is dissolved in 75 g of N-methylpyrrolidone (commercially available) while stirring under a nitrogen atmosphere. Then 3.6 g (0.026 mol) of meta-xylylenediamine are added and the clear mixture is warmed to 80°C.

Then 19.8 g (0.052 mol) of Desmodur T100 and a single adduct from lauryl alcohol are added dropwise under stirring so that the temperature does not exceed 85° C. within 1 hour. The reaction mixture is stirred at 80° C. for 3 hours to complete the reaction. A clear liquid product is obtained. The fraction of the urea compound in the obtained product is 23% by weight.

Comparative Example V5:

First, a single adduct according to patent document EP 1188779 is prepared from 2,4-toluylene diisocyanate (Desmodur T100, Bayer) and lauryl alcohol.

In a reaction vessel (round bottom flask equipped with a stirrer, reflux condenser and dropping funnel), 1.7 g (0.039 mol) of LiCl is dissolved in 75 g of 1-N-ethylpyrrolidone (commercially available) while stirring under a nitrogen atmosphere. Then 3.6 g (0.026 mol) of meta-xylylenediamine are added and the clear mixture is warmed to 80°C.

Then 19.8 g (0.052 mol) of Desmodur T100 and a single adduct from lauryl alcohol are added dropwise under stirring so that the temperature does not exceed 85° C. within 1 hour. The reaction mixture is stirred at 80° C. for 3 hours to complete the reaction. A clear low-viscosity product is obtained. The fraction of the urea compound in the obtained product is 23% by weight.

Comparative Example V6:

Step 1

First, 93.6 g of a single adduct according to patent document EP 1188779 was prepared by mixing polyethylene glycol monomethyl ether having a molar mass of 450 g/mol and 35% of 2,4-toluylene diisocyanate and 65% of 2,6- Prepared from a mixture of toluylenediisocyanates.

Step 2

In a four-necked flask equipped with a stirrer, dropping funnel, thermometer and reflux condenser, put 99.7 g of N-methylpyrrolidone (commercially available from BASF), warm to 100° C., and when this temperature is reached, 4.2 g of lithium chloride is added. The lithium chloride is then dissolved under stirring at 100° C. within 1 hour. The temperature is then lowered to 80°C.

Add 10.2 g of m-xylylenediamine and homogenize the mixture. The previously prepared isocyanate adduct (step 1) is slowly added dropwise to the amine solution under stirring so that the temperature does not exceed 85° C. within 1 hour. The reaction mixture is stirred at 80° C. for 3 hours to complete the reaction. A clear yellow product is obtained. The product contains 48% by weight of the urea compound.

Comparative Example V7:

Step 1

First, 93.6 g of a single adduct according to patent document EP 1188779 was prepared by mixing polyethylene glycol monomethyl ether having a molar mass of 450 g/mol and 35% of 2,4-toluylene diisocyanate and 65% of 2,6- Prepared from a mixture of toluylenediisocyanates.

Step 2

132.0 g of dimethyl sulfoxide (commercially available from Firma Sigma Aldrich) was placed in a four-necked flask equipped with a stirrer, dropping funnel, thermometer and reflux condenser, warmed to 100° C., and when this temperature was reached, 4.2 g of lithium chloride was added. The lithium chloride is then dissolved under stirring at 100° C. within 1 hour. The temperature is then lowered to 80°C.

Add 10.2 g of m-xylylenediamine and homogenize the mixture. The previously prepared isocyanate adduct (step 1) is slowly added dropwise to the amine solution under stirring so that the temperature does not exceed 85° C. within 1 hour. The reaction mixture is stirred at 80° C. for 3 hours to complete the reaction. A clear yellow product is obtained. The product contains 43% by weight of the urea compound.

Comparative Example V8:

Step 1

First, 93.6 g of a single adduct according to patent document EP 1188779 was prepared by mixing polyethylene glycol monomethyl ether having a molar mass of 450 g/mol and 35% of 2,4-toluylene diisocyanate and 65% of 2,6- Prepared from a mixture of toluylenediisocyanates.

Step 2

In a four-necked flask equipped with a stirrer, dropping funnel, thermometer and reflux condenser, put 99.7 g of N-ethylpyrrolidone (commercially available from BASF), warm to 100° C., and when this temperature is reached, 4.2 g of lithium chloride is added. The lithium chloride is then dissolved under stirring at 100° C. within 1 hour. The temperature is then lowered to 80°C.

Add 10.2 g of m-xylylenediamine and homogenize the mixture. The previously prepared isocyanate adduct (step 1) is slowly added dropwise to the amine solution under stirring so that the temperature does not exceed 85° C. within 1 hour. The reaction mixture is stirred at 80° C. for 3 hours to complete the reaction. A clear yellow product is obtained. The product contains 50% by weight of the urea compound.

Comparative Example V11:

Step 1

First, 64.4 g of a diisocyanate-monoadduct according to patent document EP 1188779 was mixed with polyethylene glycol monobutyl ether having a hydroxyl value of 220 mg KOH/g (measured according to DIN / ISO 4629) and 35% of 2, Prepared from a mixture of 4-toluylenediisocyanate and 65% 2,6-toluylenediisocyanate.

Step 2

Prepare a four-necked flask equipped with a stirrer, dropping funnel, thermometer and reflux condenser. 118.2 g of methyl-5-(dimethylamino)-2-methyl-5-oxopentanoate was added, and the mixture was heated to 120° C. under stirring under a nitrogen atmosphere. 4.2 g of lithium chloride are added and dissolved under stirring at this temperature for 1 hour. The temperature is then lowered to 80°C. Add 10.2 g of m-xylylenediamine and homogenize the mixture.

The isocyanate adduct prepared previously (step 1) is slowly added dropwise to the amine solution under stirring so that the temperature does not exceed 85° C. within 1 hour. The reaction mixture is stirred at 80° C. for another 3 hours to complete the reaction. A clear yellow product is obtained. The amine titer is 1 mg KOH/g (determined according to DIN 16945). The product contains 38% by weight of the urea compound.

Comparative Example V12:

Step 1

First, 64.4 g of a diisocyanate-monoadduct according to patent document EP 1188779 was mixed with polyethylene glycol monobutyl ether having a hydroxyl value of 220 mg KOH/g (measured according to DIN / ISO 4629) and 35% of 2, Prepared from a mixture of 4-toluylenediisocyanate and 65% 2,6-toluylenediisocyanate.

Step 2

Prepare a four-necked flask equipped with a stirrer, dropping funnel, thermometer and reflux condenser. Add 118.2 g of 1-(morpholin-4-yl)ethanone and warm to 120° C. under stirring under nitrogen atmosphere. 4.2 g of lithium chloride are added and dissolved under stirring at this temperature for 1 hour.

The temperature is then lowered to 80°C. Add 10.2 g of m-xylylenediamine and homogenize the mixture.

The isocyanate adduct prepared previously (step 1) is slowly added dropwise to the amine solution under stirring so that the temperature does not exceed 85° C. within 1 hour. The reaction mixture is stirred at 80° C. for another 3 hours to complete the reaction. A clear yellow product is obtained. The amine titer is 1 mg KOH/g (determined according to DIN 16945). The product contains 38% by weight of the urea compound.

Comparative Example V13: Combination of an amide compound and a urea compound not according to the present invention

In the following combination experiment, BYK-430 (30% solution of high molecular weight modified polyamide, manufactured by BYK-Chemie GmbH) is used as an amide compound not according to the present invention, similar to WO 2011/091812. This amide component was combined with a different urea compound according to the comparative example (ie a dissolved urea compound containing no amide component according to the invention as a mixing component). The mixture was stirred continuously.

The above example shows that the composition according to the invention ensures good compatibility of the corresponding urea and amide component, which leads to good productivity and at the same time better storage stability of the amide and the rheological effect composition containing urea, whereas the present invention Amide compounds not in accordance with the invention do not lead to storage-stable combinations, and therefore even simple handling as a whole composition is not possible. Therefore, in combinations not according to the invention, the introduction into the system must always be made separately, which requires more work steps and higher costs in terms of production technology.

Technical examination of the application of suitable compositions as rheological additives

Test system 1: solvent mixture consisting of n-butyl acetate and methoxypropanol

For this test series, if necessary, the content of the urea compound in the additive composition is adjusted to 28% by weight by adding an additional amount of each amide compound to the composition of all tested products. In a 100 ml glass bottle, 50 g of a solvent mixture of n-butylacetate/Dowanol PM 75:25 (w/w) is placed, followed by addition of an amount of each additive composition corresponding to 0.5% by weight of a urea compound. For this purpose, it is incorporated by means of Dispermat CV (tooth nib d = 2.5 cm at 1000 U/min) under stirring. After the addition is complete, the mixture is stirred again for 1 minute.

The samples were then placed under agitation for 1 hour and the gel strength was visually assessed as a measure of the rheological effect and compatibility of the additives based on turbidity.

Rating scale:

Gel strength 1 very strong

2 strong

3 middle

4 very weak

5 no gel

turbidity

(Compatibility): 1 sunny

2 Slightly cloudy

3 turbidity

4 strong turbidity

5 very strong turbidity

result:

According to the above results, the composition according to the present invention has better compatibility (ie, less turbidity in the system) or higher gel strength (ie, better rheological effect) compared to Comparative Example V1. ) or both gain effects.

Inspection system 2: Setalux D A 870 BA clearcoat

For this test series, if necessary, the content of the urea compound in the additive composition is adjusted to 28% by weight by adding an additional amount of each amide compound to the composition of all tested products. In a glass bottle of 100 ml, 50 g of Setalux D A 870 BA clearcoat are placed and then the respective additives are incorporated by means of Dispermat CV (serrated varnish d = 2.5 cm at 1000 U/min) under stirring. The amount of additive composition is selected to correspond to 0.4% by weight each, based on the urea compound. After the addition is complete, the mixture is stirred again for 1 minute.

The samples are then placed under agitation for 1 day, first visually evaluating the gel strength as a measure for rheological effect and then evaluating the compatibility of additives based on turbidity. The sag resistance is then tested as a measure of the rheological effect under the application conditions.

To this end, the sample is uniformly stirred with a spatula, and then applied to the contrast card at a speed of 5 cm/s with a 30-300 μm doctor blade and a BYK Gardner automatic winder. Immediately after application, hang the contrast card horizontally to dry. After drying, the layer thickness in μm is measured in the wet state, in which case the coat does not flow. In other words, neither the flowing nor the bulging is recognized. The higher the sag resistance when using the same active substance, the better the rheological effect.

Coating formulation (parts by weight):

Setalux D A 870

BA 80.0

Butyl acetate 9.9

Dowanol PMA 9.9

BYK-066 0.2

result:

The above results show that the composition according to the invention has better compatibility (ie less turbidity in the system) or high gel strength and greatly improved stability (ie maximum possible layer thickness) compared to Comparative Example V3. It is clear that it enables or represents the gain effects in combination.

Inspection System 3: Epikote 1001-X75 - Clearcoat

For this test series, if necessary, the content of the urea compound in the additive composition is adjusted to 38% by weight by adding an additional amount of each amide compound to the composition of all tested products. In a glass bottle of 100 ml, 50 g of Epikote 1001-X75 clearcoat are placed and then the respective additives are incorporated by means of Dispermat CV (serrated varnish d = 2.5 cm at 1000 U/min) under stirring. An amount corresponding to 0.8% by weight of each urea compound is selected. After the addition is complete, the mixture is stirred again for 1 minute.

The samples are then placed under agitation for 1 day, first visually evaluating the gel strength as a measure for rheological effect and then evaluating the compatibility of additives based on turbidity. The sag resistance is then tested as a measure of the rheological effect under the application conditions.

To this end, the sample is uniformly stirred with a spatula, and then applied to the contrast card at a speed of 5 cm/s with a 30-300 μm doctor blade and a BYK Gardner automatic winder. Immediately after application, hang the contrast card horizontally to dry. After drying, the layer thickness in μm is measured in the wet state, in which case the coat does not flow. In other words, neither the flowing nor the bulging is recognized. The higher the sag resistance when using the same active substance, the better the rheological effect.

Coating formulation (parts by weight):

Epikote

1001-X75 75.3

Methylisobutylketone 17.3

Isobutanol 7.4

result:

From the above results, it is clear that the composition according to the invention enables higher gel strength and greatly improved sag resistance (ie maximum possible layer thickness) at the same good compatibility compared to comparative example V3.

Inspection system 4: Worleekyd S 351 binder

In a glass bottle of 100 ml, 50 g of Worleekyd S351 binder are placed and then the respective additives are incorporated by means of Dispermat CV (tooth varnish d = 2.5 cm at 1000 U/min) under stirring. An amount corresponding to 0.7% by weight of each urea compound is selected. After the addition is complete, the mixture is stirred again for 1 minute.

The samples are then placed under agitation for 1 day and then sag resistance is evaluated as a measure of the rheological effect under the application conditions. To this end, the sample is uniformly stirred with a spatula, and then applied to the contrast card at a speed of 5 cm/s with a 50-500 μm doctor blade and an automatic winder from BYK Gardner. Immediately after application, hang the contrast card horizontally to dry. After drying, the layer thickness in μm is measured in the wet state, in which case the coat does not flow. In other words, neither the flowing nor the bulging is recognized. The higher the stability when using the same active substance, the better the rheological effect.

result:

From the above results, it is clear that the composition according to the invention enables higher gel strength and greatly improved sag resistance (ie maximum possible layer thickness) at the same good compatibility compared to comparative examples V4 and V5.

Inspection System 5: Worleekyd S 366 Clearcoat

In a glass bottle of 100 ml 50 g of Worleekyd S366 clearcoat are placed and then the respective additives are incorporated by means of Dispermat CV (serrated varnish d = 2.5 cm at 1000 U/min) under stirring. An amount corresponding to 0.5% by weight of each urea compound is selected. After the addition is complete, the mixture is stirred again for 1 minute. The samples are then placed under agitation for 1 day and then stability is evaluated as a measure of the rheological effect under the application conditions.

To this end, the sample is uniformly stirred with a spatula, and then applied to a contrast card at a speed of 5 cm/s with a 50-500 μm doctor blade and an automatic winder from BYK Gardner. Immediately after application, hang the contrast card horizontally to dry. After drying, the layer thickness in μm is measured in the wet state, in which case the coat does not flow. In other words, neither the flowing nor the bulging is recognized. The higher the sag resistance when using the same active substance, the better the rheological effect.

Coating formulation (parts by weight):

Worleekyd S 366 60% in Isopar H 80.9

Isopar H 16.0

Nuodex Combi APB 2.6

Borchi Nox M 2 0.3

BYK-066 0.2

result:

From the above results, it is clear that the composition according to the invention enables a significantly very high gel strength and a very improved sag resistance (ie maximum possible layer thickness) compared to comparative example V4.

Inspection system 6: Polystyrene Palapreg P17-02 / Palapreg H 814-01

In a 175 ml-PE-cup, first the two resin components Palapreg P 17-02 and Palapreg H 814-01 are homogenized using a Dispermat CV at 1200 U/min for 1 minute with 4 cm-tooth discs. 50 g of this mixture are then placed in a 175 ml-PE-cup and the respective additives are incorporated by means of Dispermat CV (serrated nib d = 2.5 cm at 1000 U/min) under stirring. An amount corresponding to 0.8% by weight of each urea compound is selected. After the addition is complete, the mixture is stirred again for 2 minutes.

The sample is then placed directly into a 50 ml snap cap vial and placed under agitation. After 3 days, the separation of the samples as a percentage based on the total charge is assessed and the gel strength is visually assessed as a measure for the rheological effect. The less separation of the sample, the better the rheological effect of the sample. In addition to the rheological effect, the color effect by additives also affects the formulation, but this should be as small as possible. At the same time, the higher boiling point of the amide compound is suitable for applications in the field of sheet molding compounds, since otherwise in hot pressing room air is charged and the resulting air bubbles cause unwanted entrainment of air in the pressed compound. to be.

Resin formulation (parts by weight):

Palapreg P 17-02 70

Palapreg H 814-01 30

result:

From the above results, it is clear that the composition according to the present invention significantly affects the unwanted phase separation compared to Comparative Examples V11 and V12, and the separation is effectively completely prevented as a result of the increase in gel strength.

Claims (21)

i) from 15 to 95% by weight of the amide compound (A),
ii) from 5 to 75% by weight of the urea compound (B),
iii) 0 to 50% by weight of the ionogen compound (C) and
iv) 0 to 35% by weight of organic solvent (D)
As a composition containing,
The amide compound (A) has a molar mass of 70 to 600 g/mol, the amide compound (A) includes at most one amide group in which hydrogen is bonded to a nitrogen atom, and the amide compound (A) is urethane Free from baby, phosphorus, silicon and halogen, the amide compound (A) is represented by the following formula (I):

[During the ceremony,
Xx is the same or different and is according to one of the formulas RzC(=O)-NRaRb (Xx1), RaC(=O)-NRzRb (Xx2) and RbC(=O)-NRzRa (Xx3) and is Rz, Ra and Rb and an amide group C (= O) -N combined with
Xy is the same or different and is according to one of the general formulas RzC(=O)-NRcRd(Xy1), RcC(=O)-NRzRd(Xy2) and RdC(=O)-NRzRc(Xy3) and Rz, Rc and Rd is an amide group C (= O) -N combined with
each Rz is the same or different and is a branched or unbranched hydrocarbon radical having from 1 to 32 carbon atoms, saturated or unsaturated, which may contain an amino group, an amide group or both as groups containing heteroatoms;
Ra, Rb, Rc, and Rd are each the same or different and each independently of the other is hydrogen or an organic radical branched or unbranched, saturated or unsaturated, containing 1 to 16 carbon atoms, provided that
Ra, Rb, Rc and Rd have a total of 4 or more carbon atoms,
at most one of the residues selected from the groups Ra, Rb, Rc and Rd is in the form of hydrogen,
i) at least one of Ra and Rb together with a CO-N group bonding Ra to Rb, and ii) Rc and Rd together with a CO-N group bonding Rc to Rd is according to the following formula (α-1) and 4 to 10 can form a ring having two ring atoms, or:

,
iii) Ra and Rb together with an N-atom bonding Ra to Rb, and iv) Rc and Rd together with an N-atom bonding Rc to Rd At least one of 4 to 7 can form a ring having two ring atoms, or:

, or
Rb and Rc, respectively, taken together with the N-atom and the Rz moiety bonded to Rb and Rc, may form a ring having 5 to 7 ring atoms according to formula (γ-1):

,
Ra, Rb, Rc, Rd and Rz have a total of up to 36 carbon atoms and up to 8 heteroatoms selected from the groups N and O];
The urea compound (B) has a molecular weight of at least 350 g/mol and has at least one urea group,
The ionogen compound (C) contains cationic and anionic components and is different from the amide compound (A) and the urea compound (B);
The organic solvent (D) contains no urea groups or ionic groups, and has at most two heteroatoms selected from the group consisting of nitrogen and oxygen. According to claim 1,
i) 30 to 90% by weight of an amide compound (A),
ii) from 8 to 55% by weight of the urea compound (B),
iii) 0 to 15% by weight of the ionogen compound (C) and
iv) from 2 to 25% by weight of an organic solvent (D)
A composition containing According to claim 1, wherein 50 to 100% by weight of the amide compound (A) does not have an amide group in which a hydrogen is bonded to a nitrogen atom, and 50 to 100% by weight of the amide compound (A) is also Ra, Rb, A composition, characterized in that none of the residues from the Rc and Rd groups are represented by the formula (I) but hydrogen. The composition according to claim 1, wherein 50 to 100% by weight of the amide compound (A) is represented by the following formula (Ia):

. ◈Claim 5 was abandoned when paying the registration fee.◈ 5. The method according to claim 4, wherein 50 to 100% by weight of the amide compound (A) is represented by formula (Ia), wherein i) Ra and Rb together with an N-atom bonding Ra to Rb, and ii) Rc is Rd At least one of Rc and Rd together with the N-atom bound to is according to formula (ß-1), has up to 2 heteroatoms selected from the group consisting of O and N, branched or non-branched having 4 to 7 ring atoms A composition characterized in that it forms a branched saturated or unsaturated ring. ◈Claim 6 was abandoned when paying the registration fee.◈ The composition according to claim 4, wherein 50 to 100% by weight of the amide compound (A) is represented by the formula (Ia) in which at least one of Ra, Rb, Rc and Rd is not contained in the ring, respectively. The composition according to claim 1, characterized in that 50 to 100% by weight of the formula (I) of the amide compound (A) is represented by the formula (Ib):

(Ib). ◈Claim 8 was abandoned at the time of payment of the registration fee.◈ 8. The method according to claim 7, wherein 50 to 100% by weight of the formula (I) of the amide compound (A) is represented by the formula (Ib), wherein Rb and Rc are, respectively, an N-atom and an Rz moiety bonded to Rb and Rc. together with at most 2 heteroatoms selected from the group consisting of O and N according to formula (γ-1) and forming a branched or unbranched saturated or unsaturated ring having 5 to 7 ring atoms which, composition. 8. The method according to claim 7, wherein 50 to 100% by weight of the formula (I) of the amide compound (A) is represented by the formula (Ib), wherein i) Ra and Rb together with a CO-N group bonding Ra to Rb, and ii) at least one of Rc and Rd together with the CO-N group bonding Rc to Rd is according to formula (α-1) and has up to 2 heteroatoms selected from the group consisting of O and N and has 4 to 10 ring atoms Characterized in forming a branched or unbranched saturated or unsaturated ring having a, composition. Composition according to claim 1, characterized in that 70 to 100% by weight of the urea compound (B) has at least two urea groups or at least one urea group and at least one urethane group. The composition according to claim 1, wherein 50 to 100% by weight of the urea compound (B) is represented by the following formula (II):

[During the ceremony,
R ³¹ and R ³² are each the same or different and each independently of the other is a branched or unbranched saturated or unsaturated organic radical having at most one urea group each and at most one urethane group each and containing from 1 to 100 carbon atoms; ego,
R ³³ and R ³⁴ are each the same or different and each independently of the other is a branched or unbranched polyester radical containing 1 to 300 carbon atoms, a branched or unbranched poly containing 2 to 300 carbon atoms ether radicals, branched or unbranched polyamide radicals containing from 1 to 300 carbon atoms, polysiloxane radicals containing from 3 to 100 silicon atoms, branched or unbranched C2-C22-alkylene radicals, branched or unbranched a C3-C18-alkenylene radical, a C5-C12-arylene radical, or a branched or unbranched C7-C22 arylalkylene radical,
Z and W are each the same or different, each independently of the other is represented by NH-CO-O or NH-CO-NH,
each n is the same or different and is an integer from 1 to 150, or from 2 to 120; ◈Claim 12 was abandoned when paying the registration fee.◈ The composition according to claim 1, characterized in that 50 to 100% by weight of the urea compound (B) has a molecular weight of 2000 to 55000 and 4 to 150 urea groups, respectively. According to claim 1, wherein 50 to 100% by weight of the urea compound (B) is each represented by one of the formulas selected from the group consisting of the following formulas (IIIa), (IIIb), (IIIc) and (IIId), characterized in that which composition:

[During the ceremony,
AM is the same or different and is a linear or branched, saturated or unsaturated, aliphatic, aromatic or aliphatic-aromatic organic radical having 2 to 50 C-atoms,
AM1 and AM2 are each the same or different and each independently of the other is a linear or branched, saturated or unsaturated, aliphatic, aromatic or aliphatic-aromatic organic radical having 1 to 50 C-atoms,
IC1 and IC2 are each the same or different and each independently of the other is a linear or branched, saturated or unsaturated, aliphatic, aromatic or aliphatic-aromatic hydrocarbon radical having 2 to 40 C-atoms,
IC3 is the same or different and is a linear or branched, saturated or unsaturated, aliphatic, aromatic or aliphatic-aromatic hydrocarbon radical having from 2 to 24 carbon atoms,
RP1 and RP2 are each the same or different, each independently of the other a linear or branched, saturated or unsaturated, aliphatic, aromatic or aliphatic-aromatic organic radical having 1 to 24 C-atoms, 1 to 120 ether oxygen a polyether radical having atoms, a polyester radical having 1 to 100 ester groups, a polyamide radical having 1 to 100 amide groups, or a polysiloxane radical having 3 to 100 silicon atoms,
RP3 are the same or different, linear or branched, saturated or unsaturated, aliphatic, aromatic or aliphatic-aromatic hydrocarbon radicals having 2 to 24 C-atoms, (poly)ether radicals having 1 to 20 ether oxygen atoms , a polyamide radical having 1 to 100 amide groups, a polysiloxane radical having 3 to 100 silicon atoms, or a polyester radical having 1 to 100 ester groups,
p is the same or different and is 0 or 1.]. ◈Claim 14 was abandoned at the time of payment of the registration fee.◈ 14. The method of claim 13, wherein 70 to 100% by weight of the urea compound (B) is each represented by one of the formulas selected from the group consisting of formulas (IIIa), (IIIb), (IIIc) and (IIId), wherein AM are the same or different,

and
(CH ₂ ) _q
is selected from the group consisting of;
R _x and R _y are the same or different and at each occurrence are independently CH ₃ or hydrogen;
q is the same or different and is an integer from 2 to 12;
AM1 and AM2 are each the same or different and are n-propyl, isopropyl, butyl, isobutyl, tert-butyl, lauryl, oleyl, stearyl, polyisobutylene and poly having 2 to 40 ether oxygen atoms. ether, benzyl, methylbenzyl, cyclohexyl, carboxyalkyl, hydroxyalkyl and alkylalkoxysilane.
IC1 and IC2 are each the same or different,

and

is selected from the group consisting of
IC3 is the same or different and is selected from the group consisting of methyl, ethyl, phenyl, benzyl, cyclohexyl and stearyl;
RP1 and RP2 are each the same or different, and are branched or unbranched C1- to C18-alkyl; oleyl; benzyl; allyl; polyether radicals; polyether radicals containing structural units of ethylene oxide, propylene oxide or butylene oxide; and a polyester radical containing structural units of ε-caprolactone, δ-valerolactone or both,
RP3 is the same or different, linear or branched C1- to C18-alkylene; linear or branched C2- to C18-alkylene; polyether; and polyethers containing structural units of ethylene oxide, propylene oxide and butylene oxide and having 1 to 25 ether oxygen atoms. ◈Claim 15 was abandoned when paying the registration fee.◈ According to claim 1, wherein 70 to 100% by weight of the urea compound (B) to be prepared by the reaction of an isocyanate oligomerized by isocyanurate formation, uretdione formation or both, respectively, with a monofunctional amine. A composition, characterized in that it can. ◈Claim 16 was abandoned when paying the registration fee.◈ 9. The method according to claim 1, wherein 95 to 100% by weight, or 98 to 100% by weight of the urea compound (B) each contains at least one molecular segment of the formula (IVa) A composition characterized in that it contains no segments:

wherein Y ₁ is the same or different and is a saturated or unsaturated branched or unbranched hydrocarbon radical containing 6 to 20 carbon atoms;

wherein Y ₂ is the same or different and is a saturated or unsaturated branched or unbranched hydrocarbon radical containing 6 to 20 carbon atoms. ◈Claim 17 was abandoned when paying the registration fee.◈ The composition according to claim 1, wherein the composition contains 0.5 to 4.0% by weight of the ionogen compound (C), wherein 50 to 100% by weight of the ionogen compound (C) is a lithium- or calcium salt, or a chloride thereof; A composition characterized in that it is present as at least one of acetate and nitrate. The composition according to claim 1, which is used for rheological control or thixotroping of liquid systems. delete ◈Claim 20 was abandoned when paying the registration fee.◈ 19. The liquid system of claim 18, wherein the liquid system is used as a coating, as a paint or varnish, as a plastics formulation, as a pigment paste, as a sealing agent, as a cosmetic, as a ceramic formulation, as an adhesive formulation, as a casting compound, as a drilling fluid; A composition present as a building material formulation, as a lubricant, as a filling compound, as a printing ink or as a liquid ink. As a paint or varnish, as a plastic formulation, as a pigment paste, as a sealing formulation, as a cosmetic, as a ceramic formulation, as an adhesive formulation, as a casting compound, as a building material formulation, as a lubricant, as a drilling fluid, as a filling compound, as a printing ink Formulations present as or as a liquid ink to which 0.1 to 7.5% by weight of the composition according to any one of claims 1 to 18 have been added.